Yanwei Liu

F-53B, the commercial product of chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs), has been used in Chinese chrome plating industry for 30 years, and was recently identified in the environment, which caused great concerns. So far, limited investigations have been performed on their environmental occurrence, fate and impact. In this study, we demonstrated the wide occurrence of Cl-PFESAs and their trophic transfer behavior in marine organisms from Chinese Bohai Sea. 6:2 Cl-PFESA (<0.016-0.575 ng/g wet weight) was the dominant congener, and 8:2 Cl-PFESA (<0.022-0.040 ng/g) was occasionally detected. Compared to other perfluoroalkyl and polyfluoroalkyl substances (PFASs) of concern, the levels of Cl-PFESAs were relatively lower in marine organisms. Based on the comparative analysis of Cl-PFESA contamination in mollusk samples collected in 2010-2014, both the concentrations and detection frequencies of Cl-PFESAs tended to increase in this region. And this kind of chemicals were more vulnerable to be accumulated in marine organisms at relatively higher trophic levels. Similar to perfluorooctanesulfonate (PFOS) and the long chain perfluorinated carboxylates (PFCAs), 6:2 Cl-PFESA could be magnified along the food chain. Accordingly, the potential threat might be posed to the wildlife and human beings due to unintended exposure to Cl-PFESAs.

Redox-active quinone and nonquinone moieties represent the electron exchange capacity (EEC) of natural organic matter (NOM), playing an important role in the electron transfer link of microbes and transformation of contaminants/metal minerals. However, the corresponding transformation of quinone/phenol and their respective influence on the EECs during reduction and reoxidation remain poorly characterized. Besides, it is still controversial whether nonquinones donate or accept electrons. Herein, we demonstrated that reoxidation of NOM after reduction can form new phenolic/quinone moieties, thus increasing the EEC. The assessment for the EEC, including the electron-donating capacity (EDC) and electron-accepting capacity (EAC), of nonquinones reflects the contribution of sulfur-containing moieties with considerable EDCs and EACs. In contrast, nitrogen-containing moieties donate negligible electrons even at Eh = +0.73 V. The contributions of both thiol and amine moieties to the EEC are greatly affected by adjacent functional groups. Meanwhile, aldehydes/ketones did not display an EAC during the electron transfer process of NOM. Furthermore, substantially increased EDC at Eh from +0.61 to +0.73 V could not be fully explained using thiol and phenolic moieties, suggesting the contribution of unknown moieties with high oxidation potential. The overall findings suggest that the roles of new quinones/phenol (derived from the addition of oxygen to condensed aromatic/lignin-like components) during redox dynamic cycling and thiol species should be considered in assessing the electron transfer processes of NOM.

Tetrabromobisphenol-A/S (TBBPA/S) analogs have raised substantial concern because of their adverse effects and potential bioaccumulative properties, such as TBBPA bis(allyl ether) (TBBPA-BAE) and TBBPA bis(2,3-dibromopropyl ether) (TBBPA-BDBPE). In this study, a comprehensive method for simultaneous determination of TBBPA/S and nine novel analogs, including TBBPA-BAE, TBBPA-BDBPE, TBBPS-BDBPE, TBBPA mono(allyl ether) (TBBPA-MAE), TBBPA mono(2-bromoallyl ether) (TBBPA-MBAE), TBBPA mono(2,3-dibromopropyl ether) (TBBPA-MDBPE), TBBPS-MAE, TBBPS-MBAE, and TBBPS-MDBPE in biological samples was developed. The distribution patterns and trophic transfer properties of TBBPA/S and analogs in various biological samples collected from the Chinese Bohai Sea were then studied in detail. For the first time, TBBPA-MBAE and TBBPS-BDBPE were detected in biological samples and TBBPA-MBAE was identified as a byproduct. The concentrations of TBBPA and analogs ranged from ND (not detected or below the method detection limit) to 2782.8 ng/g lipid weight (lw), and for TBBPS and analogs ranged from ND to 927.8 ng/g lw. High detection frequencies (>86%) for TBBPA, TBBPS and TBBPA-MAE, TBBPA-MDBPE, TBBPS-MAE, TBBPS-MBAE, and TBBPS-MDBPE were obtained. Meanwhile, TBBPA, TBBPS, and these five analogs displayed trophic dilution tendencies due to significantly negative correlations between trophic levels and lipid-corrected concentrations together with the trophic magnification factors (from 0.31 to 0.55). The results also indicated the novel TBBPA-MAE, TBBPA-MBAE, TBBPA-MDBPE, TBBPS-MAE, TBBPS-MBAE, and TBBPS-MDBPE could be generated not only as byproducts, but also as the probable transformation products of commercial TBBPA/S derivatives.

Natural organic matter (NOM) exhibits a distinctive electron-donating capacity (EDC) that serves a pivotal role in the redox reactions of contaminants and minerals through the transformation of electron-donating phenolic moieties. However, the ambiguity of the molecular transformation pathways (MTPs) that engender the EDC during NOM oxidation remains a significant issue. Here, MTPs that contribute to EDC were investigated by identifying the oxidized products of phenolic model compounds and NOM samples in direct or mediated electrochemical oxidation (DEO or MEO, respectively) using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). It was found that the oxidation of newly formed phenolic-OH (ArOH) and the oxidative coupling reaction of the phenoxy radical are the main MTPs that directly contribute to EDC, in addition to the transformation of hydroquinones to quinones. Notably, the oxidative coupling reaction of ArOH contributed at least 22–42% to the EDC. Ferulic acid-like structures can also directly contribute to EDC by incorporating H2O into their acrylic substituents. Furthermore, the opening of C rings can indirectly attenuate the EDC through structural alterations in the electron-donating process of NOM. Decarboxylation can either weaken or enhance the EDC depending on the structure of the phenolic moieties in NOM. These findings suggest that the EDC of NOM is a comprehensive result of multiple NOM MTPs, involving not only ArOH oxidation but also the addition of H2O to olefinic bonds and bond-breaking reactions. Our work provides molecular evidence that aids in the comprehension of the multiple EDC-associated transformation pathways of NOM.

Bromophenols occur naturally and are used globally as man-made additives in various industrial products. They are decomposition products of many emerging organic pollutants, such as tetrabromobisphenol A, polybrominated dibenzo- p-dioxin (PBDD), polybrominated diphenyl ethers (PBDE), and others. To characterize their biotransformation pathways, bromophenol congener 2,4,6-tribromophenol, being used most frequently in the synthesis of brominated flame retardants and having the greatest environmental abundance, was selected to hydroponically expose rice plants. After exposure for 5 days, 99.2% of 2,4,6-tribromophenol was metabolized by rice. Because of the lack of relative reference standards, an effective screening strategy was used to screen for potential metabolites that were further qualitatively identified by gas and liquid chromatography combined with high-resolution mass spectrometry. Forty transformation products were confirmed or tentatively identified at different confidence levels, including 9 phase I and 31 phase II metabolites. A large number of metabolites (39) were found in rice root, and 10 of them could be translocated and detected in rice stems or leaves. Many transformation pathways were proposed, including debromination, hydroxylation, methylation, coupling reactions, sulfation, and glycosylation. It was remarkable that a total of seven hydrophobic, persistent, and toxic OH-PBDEs and PBDD/Fs were found, indicating the biotic dimeric reactions of 2,4,6-tribromophenol that occurred in the rice plants. These results improve our understanding of the transformation and environmental fates of bromophenols, and they indicate new potential sources for OH-PBDEs and PBDD/Fs in the environment, especially in food chains.